CN104693337A - Synthetic method for tetrafluoroethylene-propylene copolymer crude rubber - Google Patents
Synthetic method for tetrafluoroethylene-propylene copolymer crude rubber Download PDFInfo
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Abstract
The invention discloses a synthetic method for tetrafluoroethylene-propylene copolymer crude rubber. The synthetic method comprises the following steps: under the action of a novel oxidization-reduction initiating system consisting of a peroxide initiator and a NaCO2CH(OH)SO2Na reducer, carrying out emulsion polymerization on tetrafluoroethylene and a propylene monomer in a water/tertiary butanol mixed medium to obtain tetrafluoroethylene-propylene copolymer crude rubber; breaking the emulsion and drying to obtain the tetrafluoroethylene-propylene copolymer crude rubber. According to the synthetic method disclosed by the invention, the NaCO2CH(OH)SO2Na reducer is used to replace a common reducer of sodium sulfoxylate formaldehyde, ferrous sulfate and the like, so that the tetrafluoroethylene-propylene copolymerization keeps a high polymerization rate around the room temperature to obtain tetrafluoroethylene-propylene copolymer with high molecular weight; moreover, in a reaction process, a formaldehyde decomposer and ferric hydroxide precipitates are avoided, the product is environmentally friendly, free of color and luster and further processed and crosslinked to obtain high-performance tetrafluoroethylene-propylene copolymer crude rubber.
Description
Technical field
The present invention relates to technical field of chemical engineering, particularly relate to a kind of synthetic method of tetrafluoroethylene propylene copolymer rubber.
Background technology
Tetrafluoroethylene-propylene copolymerization can be formed based on low, the flexible multipolymer of tetrafluoroethylene (TFE) and propylene (P) alternating structure, second-order transition temperature, further sulfuration (being cross-linked) processing obtains the rubber item of excellent performance, is commonly called as 4 third viton.With ethylene-propylene copolymer (second third) rubber phase ratio, because the hydrogen atom of four in ethylene unit is replaced by fluorine atoms, 4 third viton are made to have the characteristics such as corrosion-resistant, high temperature resistant, the high insulation of viton, can at 200 DEG C of life-time service, at 230 DEG C, interval uses.The processing characteristics of 4 third viton is better than other viton, can adopt extrude, the moulding process such as mold pressing makes various O type circle, sealing member, barrier film, packing ring, valve partially, the goods such as flexible pipe, rubber roll, cable.
Japan Atomic energy research institute adopts radiation initiation method to carry out TFE-P low temperature solution polymerization the earliest.E.I.Du Pont Company has applied for first TFE-P emulsion copolymerization patent in 1969, owing to only adopting ammonium persulfate initiator, polymerization temperature is higher, rate of polymerization and molecular weight of copolymer low, and the pressure of polymerization system is higher.In order to obtain the TFE-P multipolymer of high molecular, Japan AGC company and Japan Atomic energy research institute carry out radiation and cause low temperature TFE-P emulsion copolymerization research from 20 century 70s, adopt
60the gamma-radiation radiation-initiated polymerization that Co produces.But due to irradiation, to cause operation easier and danger large, therefore has no industrializing implementation report.
Subsequently, Asahi Glass company starts the TFE-P emulsion copolymerization technological development carrying out oxidation-reduction trigger system initiation, the oxidation-reduction trigger system of the said firm's patent report forms primarily of water soluble persulfates and inorganic reducing agent, and reductive agent comprises thiosulphate, sulphite, formaldehyde sulfoxylate salt (US 4277586).In order to improve rate of polymerization further, more than in polymerization system, add ferrous salt and ethylenediamine tetraacetic acid (EDTA) (EDTA) (US 4463144).For the polymerization system adding ferrous salt, it is favourable to raising rate of polymerization that system pH maintains weakly alkaline (8.5 ~ 10).Paper (the Makromol. Chem. that the Kojima etc. of Asahi Glass company delivers, 1981, 182:1429-1439) report ammonium persulfate initiator concentration, ferrous sulfate concentration, formaldehyde sulfoxylate na concn, Perfluorocaprylic Acid ammonium concentration, polymerization temperature, system pH, t butanol content etc. are on the impact of TFE-P rate of polymerization and average molecular weight of copolymer, find that initiator concentration affects little on rate of polymerization and molecular weight of copolymer within the specific limits, and along with the increase of ferrous sulfate and sodium sulfoxylate formaldehyde reductant concentration, rate of polymerization increases gradually, and molecular weight of copolymer change is little, when emulsifier concentration increases, rate of polymerization and molecular weight of copolymer all increase.In addition, find when system pH rises to about 9 from 5, rate of polymerization constantly significantly increases, and when pH is 9 ~ 10.5, rate of polymerization maintains highest level, and when continuing to increase pH value, rate of polymerization declines rapidly again.
The nineties in 20th century, on the TFE-P bulk copolymerization Research foundation that Petrov etc. cause at peroxidized t-butyl perbenzoate (TBPB), to TBPB-FeSO
4– CH
2(OH) SO
2the TFE-P emulsion copolymerization that Na-EDTA oxidation-reduction system causes is studied (J. Polym. Sci,: Polym. Chem., 1994,32:2229 ~ 2234,2235 ~ 2239), find that this initiator system also can realize TFE-P and be polymerized in room temperature (about 25 DEG C), along with TBPB concentration increases, rate of polymerization and molecular weight of copolymer change are not quite, and along with the increase of ferrous sulfate and formaldehyde sulfoxylate na concn, rate of polymerization increases, and molecular weight of copolymer slightly declines; Along with ammonium perfluorocaprylate emulsifier concentration increases, rate of polymerization increases, and molecular weight of copolymer first increases and tends to balance.Adopt organic peroxide evocating agent can improve the thermostability of TFE-P multipolymer to a certain extent.
As can be seen here, in order to obtain the TFE-P multipolymer rubber of high molecular, polymerization temperature can not be too high, therefore patent and bibliographical information many employings oxidation-reduction trigger system initiated polymerization, to obtain higher rate of polymerization.And most oxidation-reduction trigger system comprises sodium sulfoxylate formaldehyde and/or ferrous salt, sodium sulfoxylate formaldehyde can decompose generation formaldehyde in polymerization or dry last handling process, be discharged into environment or be included in rubber, affect the wholesomeness of goods, be difficult to the service requirements of satisfied high-grade goods.Ferrous ions generates iron ion, and can form ironic hydroxide dark precipitate in the basic conditions, this throw out is included in TFE-P copolymer emulsion and rubber, and goods can be made to have color and luster.
For above problem, the present invention proposes a kind of method that initiator system be made up of organo-peroxide and novel reducer causes TFE-P emulsion copolymerization, the molecular formula of reductive agent is NaCO
2cH (OH) SO
2na, developed by German Bruggenemann Chemical company and patent production, the trade mark is Bruggolite FF6M, after this reductive agent and peroxide initiator combine, have and combine trigger rate faster than identical initiator and sodium sulfoxylate formaldehyde, be applicable to the polyreaction of wide ph range, reaction process does not produce formaldehyde, can reduce the generation of volatile organic matter (VOC), be a kind of environment-friendly type reductive agent.Oxidation-reduction trigger system of the present invention is adopted to carry out TFE-P emulsion copolymerization, the quick letex polymerization of TFE-P can be realized under the condition that simplification oxidation-reduction system composition, reduction initiator amount and VOC produce, obtain the TFE-P multipolymer rubber of high molecular, high-quality.
Summary of the invention
The object of this invention is to provide a kind of synthetic method of tetrafluoroethylene propylene copolymer rubber.
A kind of synthetic method of tetrafluoroethylene propylene copolymer rubber is: add in autoclave by 1000 grams of deionized waters, the 20-100 gram trimethyl carbinol, 1.5 ~ 5.0 grams of ammonium perfluorocaprylates, 0.5 ~ 2.5 gram of peroxide initiator, after nitrogen deoxygenation is filled in sealing, stir and be warming up to 20 ~ 40
oc, once or continuously adding in still with initiator mol ratio is the NaCO of 2/1 ~ 1/2
2cH (OH) SO
2the Na aqueous solution, pump in still simultaneously mol ratio be 80/20 ~ 70/30 initial tetrafluoroethylene/propylene mix monomer to still internal pressure reach set(ting)value between 1.5 ~ 2.5MPa, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 60/40 ~ 50/50 supplementary tetrafluoroethylene/propylene mix monomer reach set(ting)value to pressure, and after pressure again decline 0.1MPa, pump into supplementary tetrafluoroethylene/propylene mix monomer, repeat above mix monomer and supplement process, to supplement or after reductive agent dropwises when reaching 20 ~ 30 monomers, terminate mix monomer to add, after being polymerized to pressure drop 0.5MPa, get rid of residual monomer, terminate polymerization, obtain tetrafluoroethylene propylene copolymer latex, in tetrafluoroethylene propylene copolymer latex, add flocculation agent makes latex breakdown of emulsion condense, and condensation product after filtration, deionized water wash, drying obtain tetrafluoroethylene propylene copolymer rubber.
Described peroxide initiator is peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, peroxidation tert-butyl acetate, peroxidation acetic acid tert-pentyl ester, peroxidation 3,5,5-trimethylhexanoate, peroxidation 3,5,5-tri-methyl hexanoic acid tert-pentyl ester, tert-butylperoxy isopropyl carbonate, the peroxidation 2-ethylhexyl carbonate tert-butyl ester or peroxidation 2-ethylhexyl carbonate tert-pentyl ester.
Described flocculation agent is sodium-chlor, calcium chloride, magnesium chloride, aluminum chloride, sodium sulfate or Tai-Ace S 150.
The present invention adopts NaCO
2cH (OH) SO
2na reductive agent substitutes the conventional reductive agent such as sodium sulfoxylate formaldehyde, ferrous sulfate of TFE-P emulsion copolymerization, not only can maintain high rate of polymerization near room temperature, obtain the TFE-P multipolymer rubber of high molecular, and the formaldehydeless resolvent of reaction process and bulky ferric hydroxide precipitate produce, the wholesomeness of product is good, color and luster is little, can process and obtain high performance TFE-P copolymer rubber.
Embodiment
The synthesis of TFE-P multipolymer adopts emulsion polymerisation process to carry out, and reaction medium, based on deionized water, meanwhile, in order to improve the solvability of initiator and monomer, suitably adds the t-butanol solvent of dissolving each other with water.Emulsifying agent adopts ammonium perfluorocaprylate, and can play colloid provide protection to the copolymer particle formed, obtain stable emulsion, its consumption is 0.15 ~ 0.50% (relative deionized water).
The peroxide initiator adopted is that in benzene, 10 hr half-life temperature are 100
othe oil-soluble organic peroxide initiator of about C, comprise peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, peroxidation tert-butyl acetate, peroxidation acetic acid tert-pentyl ester, peroxidation 3,5,5-trimethylhexanoate, peroxidation 3,5,5-tri-methyl hexanoic acid tert-pentyl ester, tert-butylperoxy isopropyl carbonate, the peroxidation 2-ethylhexyl carbonate tert-butyl ester, peroxidation 2-ethylhexyl carbonate tert-pentyl ester, its consumption is 0.05 ~ 0.25% of deionized water quality.
In order to improve the rate of decomposition of initiator, meeting the needs of room temperature TFE-P letex polymerization, adding NaCO
2cH (OH) SO
2na novel reducer, this reductive agent is water-soluble, can be disposable or add continuously as an aqueous solution after reactor seals deoxygenation, general when polymerization temperature setting lower (as 20 ~ 25
oc), time, reductive agent can disposablely add, and when polymerization temperature setting higher time (25 ~ 40
oc), time, reductive agent can add continuously.The mol ratio of reductive agent consumption and initiator amount is 1/2 ~ 2/1.
In order to obtain the large TFE-P multipolymer rubber of molecular weight, setting polymerization temperature is 20 ~ 40
oc, polymerization temperature is too high, and the molecular weight of the TFE-P multipolymer obtained is on the low side, after processing sulfuration the tensile strength of rubber and rebound resilience on the low side.Polymerization temperature is too low, and polymerization rate reduces, and oxidation-reduction trigger system consumption is bigger than normal.
TFE and P is gaseous monomer, need be driven in polymeric kettle by high-pressure pump after starting polymerization, the mol ratio of the TFE/P monomer wherein added first is between 80/20 ~ 70/30, in advance two kinds of monomers can be pressed setting mixed in molar ratio, then, under waiting polymerization system to be warmed up to design temperature, join in polymeric kettle.Add TFE/P mix monomer to still internal pressure first and reach initial set value between 1.5 ~ 2.5MPa, after polymerization starts certain hour, still internal pressure declines, when after pressure drop 0.1MPa (relative initial set value), pump into mol ratio be 60/40 ~ 50/50 supplementary TFE/P mix monomer reach set(ting)value again to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, to supplement or after reductive agent dropwises when reaching 20 ~ 30 monomers, terminate mix monomer to add, after continuing to be polymerized to pressure drop 0.5MPa (relative initial setting force value), get rid of unreacted monomer and terminate polymerization, TFE-P copolymer emulsion can be obtained.
In TFE-P copolymer emulsion, add inorganic salt flocculation agent, latex breakdown of emulsion is condensed, condensation product after filtration, deionized water wash, drying obtain tetrafluoroethylene propylene copolymer rubber.The inorganic salt flocculation agent adopted is sodium-chlor, magnesium chloride, calcium chloride, aluminum chloride, sodium sulfate, Tai-Ace S 150, and flocculation agent add-on is as the criterion completely with emulsion condensation.
Embodiment 1
1000 grams of deionized waters, 40 grams of trimethyl carbinols, 2.0 grams of ammonium perfluorocaprylates, 2.0 grams of (0.0103mol) peroxidized t-butyl perbenzoate initiators are added in autoclave, after nitrogen deoxygenation is filled in sealing, stirs and be warming up to 25
oc, once adds containing 1.689 grams of (0.0103mol) NaCO in still
2cH (OH) SO
2the aqueous solution of Na, pump in still mol ratio be 80/20 initial TFE/P mix monomer reach 2.0MPa to still internal pressure, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 60/40 supplementary TFE/P mix monomer reach 2.0MPa to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, when reaching after 20 monomers supplement, terminating mix monomer and adding, be polymerized to pressure drop to 1.5MPa, get rid of residual monomer, terminate polymerization, obtain TFE-P copolymer emulsion; In copolymer emulsion, add the cohesion of aluminum chloride breakdown of emulsion, condensation product after filtration, deionized water wash, drying obtain TFE-P multipolymer rubber.
Embodiment 2
1000 grams of deionized waters, 20 grams of trimethyl carbinols, 2.5 grams of ammonium perfluorocaprylates, 2.5 grams of (0.0096mol) peroxidation 2-ethylhexyl carbonate tert-pentyl ester initiators are added in autoclave, after nitrogen deoxygenation is filled in sealing, stirs and be warming up to 20
oc, once adds containing 3.15 grams of (0.0192mol) NaCO in still
2cH (OH) SO
2the aqueous solution of Na, pump in still mol ratio be 80/20 initial TFE/P mix monomer reach 2500KPa to still internal pressure, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 60/40 supplementary TFE/P mix monomer reach 2.5MPa to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, when reaching after 25 monomers supplement, terminating mix monomer and adding, be polymerized to pressure drop to 2.0KPa, get rid of residual monomer, terminate polymerization, obtain TFE-P copolymer emulsion; In copolymer emulsion, add the cohesion of sodium-chlor breakdown of emulsion, condensation product after filtration, deionized water wash, drying obtain TFE-P multipolymer rubber.
Embodiment 3
1000 grams of deionized waters, 60 grams of trimethyl carbinols, 1.5 grams of ammonium perfluorocaprylates, 2.46 grams of (0.010mol) peroxidation 2-ethylhexyl carbonate tert-butyl ester initiators are added in autoclave, after nitrogen deoxygenation is filled in sealing, stirs and be warming up to 25
oc, once adds containing 1.64 grams of (0.010mol) NaCO in still
2cH (OH) SO
2the aqueous solution of Na, pump in still mol ratio be 70/30 initial TFE/P mix monomer reach 2.0MPa to still internal pressure, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 55/45 supplementary TFE/P mix monomer reach 2.0MPa to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, when reaching after 20 monomers supplement, terminating mix monomer and adding, be polymerized to pressure drop to 1.5MPa, get rid of residual monomer, terminate polymerization, obtain TFE-P copolymer emulsion; In copolymer emulsion, add the cohesion of calcium chloride breakdown of emulsion, condensation product after filtration, deionized water wash, drying obtain TFE-P multipolymer rubber.
Embodiment 4
1000 grams of deionized waters, 80 grams of trimethyl carbinols, 2.0 grams of ammonium perfluorocaprylates, 2.44 grams of (0.010mol) peroxidation 3,5,5 Trimethylhexanoic acid tert-pentyl ester initiators are added in autoclave, after nitrogen deoxygenation is filled in sealing, stirs and be warming up to 25
oc, once adds containing 1.64 grams of (0.010mol) NaCO in still
2cH (OH) SO
2the aqueous solution of Na, pump in still mol ratio be 80/20 initial TFE/P mix monomer reach 2.0MPa to still internal pressure, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 50/50 supplementary TFE/P mix monomer reach 2.0MPa to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, when reaching after 20 monomers supplement, terminating mix monomer and adding, be polymerized to pressure drop to 1.5MPa, get rid of residual monomer, terminate polymerization, obtain TFE-P copolymer emulsion; In copolymer emulsion, add the cohesion of magnesium chloride breakdown of emulsion, condensation product after filtration, deionized water wash, drying obtain TFE-P multipolymer rubber.
Embodiment 5
1000 grams of deionized waters, 100 grams of trimethyl carbinols, 2.0 grams of ammonium perfluorocaprylates, 2.30 grams of (0.010mol) peroxidation 3,5,5 Trimethylhexanoic acid tert-butyl ester initiators are added in autoclave, after nitrogen deoxygenation is filled in sealing, stirs and be warming up to 25
oc, once adds containing 1.64 grams of (0.010mol) NaCO in still
2cH (OH) SO
2the aqueous solution of Na, pump in still mol ratio be 80/20 initial TFE/P mix monomer reach 2.0MPa to still internal pressure, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 55/45 supplementary TFE/P mix monomer reach 2.0MPa to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, when reaching after 25 monomers supplement, terminating mix monomer and adding, be polymerized to pressure drop to 1.5MPa, get rid of residual monomer, terminate polymerization, obtain TFE-P copolymer emulsion; In copolymer emulsion, add the cohesion of sodium sulfate breakdown of emulsion, condensation product after filtration, deionized water wash, drying obtain TFE-P multipolymer rubber.
Embodiment 6
1000 grams of deionized waters, 40 grams of trimethyl carbinols, 5.0 grams of ammonium perfluorocaprylates, 1.0 grams of (0.00756mol) peroxidation tert-butyl acetate initiators are added in autoclave, after nitrogen deoxygenation is filled in sealing, stirs and be warming up to 35
oc, adds continuously containing 2.48 grams of (0.01513mol) NaCO in still
2cH (OH) SO
2the aqueous solution of Na, pump in still mol ratio be 80/20 initial TFE/P mix monomer reach 2.0MPa to still internal pressure, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 55/45 supplementary TFE/P mix monomer reach 2.0MPa to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, after the water-soluble liquid pump of reductive agent adds end, mix monomer is stopped to add, be polymerized to pressure drop to 1.5MPa, get rid of residual monomer, terminate polymerization, obtain TFE-P copolymer emulsion, in copolymer emulsion, add the cohesion of Tai-Ace S 150 breakdown of emulsion, condensation product after filtration, deionized water wash, drying obtain TFE-P multipolymer rubber.
Embodiment 7
1000 grams of deionized waters, 40 grams of trimethyl carbinols, 2.0 grams of ammonium perfluorocaprylates, 0.50 gram of (0.00284mol) tert-butylperoxy isopropyl carbonate initiator are added in autoclave, after nitrogen deoxygenation is filled in sealing, stirs and be warming up to 40
oc, adds continuously containing 0.93 gram of (0.00568mol) NaCO in still
2cH (OH) SO
2the aqueous solution of Na, pump in still mol ratio be 80/20 initial TFE/P mix monomer reach 2.0MPa to still internal pressure, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 50/50 supplementary TFE/P mix monomer reach 2.0MPa to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, after the water-soluble liquid pump of reductive agent adds end, mix monomer is stopped to add, be polymerized to pressure drop to 1.5MPa, get rid of residual monomer, terminate polymerization, obtain TFE-P copolymer emulsion, in copolymer emulsion, add the cohesion of calcium chloride breakdown of emulsion, condensation product after filtration, deionized water wash, drying obtain TFE-P multipolymer rubber.
Embodiment 8
1000 grams of deionized waters, 50 grams of trimethyl carbinols, 2.5 grams of ammonium perfluorocaprylates, 1.46 grams of (0.010mol) peroxidation acetic acid tert-pentyl ester initiators are added in autoclave, after nitrogen deoxygenation is filled in sealing, stirs and be warming up to 35
oc, adds continuously containing 0.82 gram of (0.005mol) NaCO in still
2cH (OH) SO
2the aqueous solution of Na, pump in still mol ratio be 80/20 initial TFE/P mix monomer reach 2.0MPa to still internal pressure, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 55/45 supplementary TFE/P mix monomer reach 2.0Mp to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, after the water-soluble liquid pump of reductive agent adds end, mix monomer is stopped to add, be polymerized to pressure drop to 1.5MPa, get rid of residual monomer, terminate polymerization, obtain TFE-P copolymer emulsion, in copolymer emulsion, add the cohesion of calcium chloride breakdown of emulsion, condensation product after filtration, deionized water wash, drying obtain TFE-P multipolymer rubber.
Embodiment 9
1000 grams of deionized waters, 40 grams of trimethyl carbinols, 2.0 grams of ammonium perfluorocaprylates, 2.08 grams of (0.010mol) peroxide acid tert-amyl acetate initiators are added in autoclave, after nitrogen deoxygenation is filled in sealing, stirs and be warming up to 25
oc, once adds containing 1.64 grams of (0.010mol) NaCO in still
2cH (OH) SO
2the aqueous solution of Na, pump in still mol ratio be 80/20 initial TFE/P mix monomer reach 2.0MPa to still internal pressure, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 60/40 supplementary TFE/P mix monomer reach 2.0MPa to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, when reaching after 30 monomers supplement, terminating mix monomer and adding, be polymerized to pressure drop to 1.5MPa, get rid of residual monomer, terminate polymerization, obtain TFE-P copolymer emulsion; In copolymer emulsion, add the cohesion of calcium chloride breakdown of emulsion, condensation product after filtration, deionized water wash, drying obtain TFE-P multipolymer rubber.
Embodiment 10
1000 grams of deionized waters, 40 grams of trimethyl carbinols, 1.8 grams of ammonium perfluorocaprylates, 1.94 grams of (0.010mol) peroxidized t-butyl perbenzoate initiators are added in autoclave, after nitrogen deoxygenation is filled in sealing, stirs and be warming up to 28
oc, once adds containing 1.64 grams of (0.010mol) NaCO in still
2cH (OH) SO
2the aqueous solution of Na, pump in still mol ratio be 80/20 initial TFE/P mix monomer reach 2.0MPa to still internal pressure, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 50/50 supplementary TFE/P mix monomer reach 2.0MPa to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, when reaching after 25 monomers supplement, terminating mix monomer and adding, be polymerized to pressure drop to 1.5MPa, get rid of residual monomer, terminate polymerization, obtain TFE-P copolymer emulsion; In copolymer emulsion, add the cohesion of calcium chloride breakdown of emulsion, condensation product after filtration, deionized water wash, drying obtain TFE-P multipolymer rubber.
Embodiment 11
1000 grams of deionized waters, 40 grams of trimethyl carbinols, 2.0 grams of ammonium perfluorocaprylates, 2.08 grams of (0.010mol) peroxide acid tert-amyl acetate initiators are added in autoclave, after nitrogen deoxygenation is filled in sealing, stirs and be warming up to 32
oc, once adds containing 1.64 grams of (0.010mol) NaCO in still
2cH (OH) SO
2the aqueous solution of Na, pump in still mol ratio be 75/25 initial TFE/P mix monomer reach 1.8MPa to still internal pressure, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 55/45 supplementary TFE/P mix monomer reach 1.8MPa to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, when reaching after 30 monomers supplement, terminating mix monomer and adding, be polymerized to pressure drop to 1.3MPa, get rid of residual monomer, terminate polymerization, obtain TFE-P copolymer emulsion; In copolymer emulsion, add the cohesion of sodium-chlor breakdown of emulsion, condensation product after filtration, deionized water wash, drying obtain TFE-P multipolymer rubber.
Embodiment 12
1000 grams of deionized waters, 40 grams of trimethyl carbinols, 2.0 grams of ammonium perfluorocaprylates, 2.08 grams of (0.010mol) peroxide acid tert-amyl acetate initiators are added in autoclave, after nitrogen deoxygenation is filled in sealing, stirs and be warming up to 25
oc, once adds containing 1.64 grams of (0.010mol) NaCO in still
2cH (OH) SO
2the aqueous solution of Na, pump in still mol ratio be 80/20 initial TFE/P mix monomer reach 1.5MPa to still internal pressure, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 55/45 supplementary TFE/P mix monomer reach 1.5MPa to pressure, and after pressure again decline 0.1MPa, pump into supplementary TFE/P mix monomer, repeat above mix monomer and supplement process, when reaching after 30 monomers supplement, terminating mix monomer and adding, be polymerized to pressure drop to 1.0MPa, get rid of residual monomer, terminate polymerization, obtain TFE-P copolymer emulsion; In copolymer emulsion, add the cohesion of sodium sulfate breakdown of emulsion, condensation product after filtration, deionized water wash, drying obtain TFE-P multipolymer rubber.
Claims (3)
1. the synthetic method of a tetrafluoroethylene propylene copolymer rubber, it is characterized in that: 1000 grams of deionized waters, the 20-100 gram trimethyl carbinol, 1.5 ~ 5.0 grams of ammonium perfluorocaprylates, 0.5 ~ 2.5 gram of peroxide initiator are added in autoclave, after nitrogen deoxygenation is filled in sealing, stir and be warming up to 20 ~ 40
oc, once or continuously adding in still with initiator mol ratio is the NaCO of 2/1 ~ 1/2
2cH (OH) SO
2the Na aqueous solution, pump in still simultaneously mol ratio be 80/20 ~ 70/30 initial tetrafluoroethylene/propylene mix monomer to still internal pressure reach set(ting)value between 1.5 ~ 2.5MPa, start polymerization, when after still internal pressure decline 0.1MPa, pump into mol ratio be 60/40 ~ 50/50 supplementary tetrafluoroethylene/propylene mix monomer reach set(ting)value to pressure, and after pressure again decline 0.1MPa, pump into supplementary tetrafluoroethylene/propylene mix monomer, repeat above mix monomer and supplement process, to supplement or after reductive agent dropwises when reaching 20 ~ 30 monomers, terminate mix monomer to add, after being polymerized to pressure drop 0.5MPa, get rid of residual monomer, terminate polymerization, obtain tetrafluoroethylene propylene copolymer latex, in tetrafluoroethylene propylene copolymer latex, add flocculation agent makes latex breakdown of emulsion condense, and condensation product after filtration, deionized water wash, drying obtain tetrafluoroethylene propylene copolymer rubber.
2. the synthetic method of a kind of tetrafluoroethylene propylene copolymer rubber according to claim 1, it is characterized in that described peroxide initiator is peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, peroxidation tert-butyl acetate, peroxidation acetic acid tert-pentyl ester, peroxidation 3,5,5-trimethylhexanoate, peroxidation 3,5,5-tri-methyl hexanoic acid tert-pentyl ester, tert-butylperoxy isopropyl carbonate, the peroxidation 2-ethylhexyl carbonate tert-butyl ester or peroxidation 2-ethylhexyl carbonate tert-pentyl ester.
3. the synthetic method of a kind of tetrafluoroethylene propylene copolymer rubber according to claim 1, is characterized in that described flocculation agent is sodium-chlor, calcium chloride, magnesium chloride, aluminum chloride, sodium sulfate or Tai-Ace S 150.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4277586A (en) * | 1974-11-20 | 1981-07-07 | Asahi Glass Company, Ltd. | Process for preparing a propylene-tetrafluoroethylene copolymer |
| CN86105039A (en) * | 1985-08-05 | 1987-02-11 | 奥西蒙特公司 | Composition be total to hardened fluoroelastomer of promoting chemical stability |
| CN1031238A (en) * | 1987-08-10 | 1989-02-22 | 森陶硝子株式会社 | The manufacture method of graft polymerized flexible fluororesin |
| CN1408735A (en) * | 2001-09-27 | 2003-04-09 | 旭硝子株式会社 | process for preparing polymer containing fluorine |
-
2015
- 2015-01-21 CN CN201510029291.1A patent/CN104693337A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4277586A (en) * | 1974-11-20 | 1981-07-07 | Asahi Glass Company, Ltd. | Process for preparing a propylene-tetrafluoroethylene copolymer |
| CN86105039A (en) * | 1985-08-05 | 1987-02-11 | 奥西蒙特公司 | Composition be total to hardened fluoroelastomer of promoting chemical stability |
| CN1031238A (en) * | 1987-08-10 | 1989-02-22 | 森陶硝子株式会社 | The manufacture method of graft polymerized flexible fluororesin |
| CN1408735A (en) * | 2001-09-27 | 2003-04-09 | 旭硝子株式会社 | process for preparing polymer containing fluorine |
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